The reaction of 2‐phenoxy‐3,5‐dinitropyridine with substituted anilines in the presence of 1,4‐diazabicyclo[2.2.2]octane in dimethyl sulfoxide: Kinetic and equilibrium studies

The reactions of 2‐phenoxy‐3,5‐dinitropyridine ( 1 ) with a series of substituted anilines ( 4a–d ) in dimethyl sulfoxide (DMSO) in the presence of 1,4‐diazabicyclo2.2.2]octane (DABCO) yield the 2‐anilino derivatives without the accumulation of intermediates. The kinetics is compatible with a two‐step reaction involving initial nucleophilic attack followed by either base‐catalyzed or uncatalyzed conversion to the product. The base‐catalyzed pathway is likely to involve rate‐limiting proton transfer from the zwitterionic intermediate to base. The results are compared with those for reactions of 1,3,5‐trinitrobenzene (2) and phenyl 2,4,6‐trinitrophenyl ether ( 3 , R = Ph ) with anilines. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 198–203, 2009